Abstract Polyimides (PI) synthesized from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with various diamines have been frequently studied as gas separation membranes. The use of 6FDA in polyimides creates a bent structure than can increase fractional free volume (FFV) and gas permeability. Here, we demonstrate that 6FDA is also a useful building block for PI‐ionene materials, which contain cations directly within the polymer backbone. These new 6FDA‐containing PI‐ionenes were combined with several different imidazolium ionic liquids (ILs) to form thin membranes. The thermal properties of all the derivatives were investigated to determine the relationship between regiochemistry and degradation as well as the intermolecular forces that are present within these structures. The gas separation properties of these 6FDA‐containing PI‐ionene + IL materials were investigated, showing modest CO2permeabilities similar to other polyimide‐ionenes and CO2/CH4and CO2/N2permselectivities that were relatively higher than other polyimide‐ionenes.
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Poly(propylene glycol)‐Based Non‐Isocyanate Polyurethane Ionenes: Thermal, Morphological and Conductive Properties
Abstract The synthesis and characterization of a series of polyurethane ionenes using a non‐isocyanate approach is disclosed. Imidazole‐capped, urethane‐containing prepolymers are prepared by first reacting carbonyl diimidazole (CDI) with several poly(propylene glycol) (PPG) diols with variable molecular weight, followed by subsequent reaction with 3‐aminopropylimidazole (API). Polymerization with 1,4‐dibromomethylbenzene followed by anion exchange resulted in the desired polyurethane ionenes bearing the [NTf2] counteranion as a series of viscous liquids. NMR and FTIR spectroscopy are used to characterize the intermediates and final ionenes, including molecular weight determination by end‐group analysis. A single glass transition temperature (Tg), as determined by differential scanning calorimetry (DSC), is observed for each ionene (−38 to −64 °C) with theTgdecreasing with increasing PPG molecular weight. Thermogravimetric analysis (TGA) indicated a two‐step decomposition for each ionene, with the first being degradation of the PPG segment, followed by the urethane/ionic segment. Microphase separation is observed from x‐ray scattering profiles with Bragg distances that increased with increasing PPG molecular weight. Ionic conductivity is found to be inversely dependent upon DSCTgat lower temperatures (RT and below); however, at higher temperatures, conductivity appears to be more dependent upon the ability of ionic aggregates caused by phase separation to interact.
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- Award ID(s):
- 2104375
- PAR ID:
- 10508897
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Macromolecular Chemistry and Physics
- Volume:
- 224
- Issue:
- 22
- ISSN:
- 1022-1352
- Subject(s) / Keyword(s):
- ionene, non-isocyanate, polyurethane, structure-activity relationship
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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